Polymer bound (pentahaptocyclopentadienyl)biscarbonyl rhodium hydroformylation catalyst

ABSTRACT

A catalyst having the structural formula ##STR1## wherein R is zero or an alkyl having from 1 to 10 carbon atoms and wherein  P  is a polystyrene polymer backbone, where the 6-member ring is part of the polymer. The catalyst is useful for converting olefins to aldehydes in high yield under reaction temperatures of from about 90° to 140° C. and pressures of about 300 to about 5000 psig in the presence of hydrogen and carbon monoxide yielding gases, and preferably polymer swelling solvents such as benzene, THF and toluene. The catalyst is also useful in hydrogenation reactions.

This application is a divisional of Ser. No. 877,440, filed Feb. 13,1978.

This invention relates to the synthesis of a novel polymer boundrhodium-containing catalyst. More particularly, this invention relatesto the synthesis and catalytic activity of a novel polymer boundrhodium-containing hydroformylation catalyst containing the activerhodium as a (pentahaptocyclopentadienyl)biscarbonyl complex bound tothe polymer.

Hydroformylation of terminal olefins by homogeneous rhodium catalysts iswell-known in the art. Representative examples of references describingthe types of rhodium catalysts used in hydroformylation reaction andreaction conditions are U.S. Pat. Nos. 3,917,661; 3,907,847; 3,821,311;3,499,932; 3,527,809; 3,825,601; 3,948,999; and 3,984,478. Literaturereferences include Tetrahedron Letters, 1971 (50) 4787-90 Grubbs, etal.; J. Macromol. Sci., Chem, 1973, 7 (5), 1047-63; Inorg. Chem. Acta,1975, 12 (1), 15-21, Grubbs, et al.; Polym. Prepr. ACS Div. PolymerChem., 1972, 13 (12), 828-32; and Japan Kokai No. 76 06,890. While thesereferences are not exhaustive of the art, they appear to berepresentative of hydroformylation in the current state of this art.However, these catalysts and reactions are generally poor when used withinternal olefins. In addition, the catalysts disclosed in the referencedpatents are extremely difficult to recover from the reaction. Thisrecovery is important since rhodium is an extremely expensive metal andthe product cost rises sharply with each percentage drop in rhodiumrecovery from a previous reaction. Additionally, these catalysts usuallyemploy very toxic ligands such as Group V materials, phosphines,phosphites, arsines, arsinites and organoantimony compounds.

Hydroformylation is a reaction which, converts olefins (equivalent toalkenes for the purposes of this specification to aldehydes such asshown in the formula below. ##STR2## wherein R is hydrogen or an alkyl.

Usually the hydroformylation procedure is followed by the hydrogenationof aldehydes to produce alcohols. This procedure is relatively simpleand can be carried out by any one of several well-known means. The mostdifficult and least efficient step is the initial hydroformylationconversion of olefins to aldehydes. In the art cited above, suchconversions have been accomplished, but only using catalysts which aredifficult to recover, and in some cases are extremely toxic.

It would therefore be of great benefit to provide a catalyst which hashigh levels of activity for the conversion of olefins to aldehyde,employs non-toxic materials, and is readily recovered.

It is therefore an object of the present invention to provide asynthesis and catalyst for hydroformylation reactions which isrecoverable and reuseable. Other objects will become apparent to thoseskilled in this art as the description proceeds.

It has now been discovered according to the present invention that acatalyst having the general structure ##STR3## wherein R is zero or analkyl group containing from 1 to 10 carbon atoms, and where P representsa polystyrene polymer backbone, the 6-member ring being part of thepolymer, is an effective catalyst for the hydroformylation conversion ofolefins to aldehydes. The catalyst is effective under conversionconditions wherein the temperature ranges from about 90° C. to about140° C. and pressures of from about 300 to about 5,000 pounds per squareinch gauge (psig). Higher temperatures are possible as the pressureexceeds 2,500 psig. High temperatures without sufficient pressure willgenerally deactivate the catalyst. The reaction is carried out in thepresence of mixtures of hydrogen and carbon monoxide. Normally the ratioof hydrogen to carbon monoxide will range from about 80/20 to about20/80 although from about 60/40 to about 50/50, respectively, ispreferred.

The catalyst of the instant invention is an unique polymer bound(pentahaptocyclopentadienyl) biscarbonylrhodium compound useful inhydroformylation reactions. The material is effective for both internaland primary olefins and does not employ a potentially toxic group Vligand. The catalyst is also effective for the hydrogenation of thealdehyde produced by hydroformylation to form alcohols.

The polystyrene polymer to which the active rhodium catalyst complex isbonded can be any polymer of sufficient molecular weight to contain thelevels of rhodium desired in the reaction being carried out. Normally,however, the polymer will have a molecular weight of at least 4,000.Generally polymers having a molecular weight of 4,000 to 100,000 aremost preferred. Representative examples of acceptable polystyrenepolymers are Biorad SX-1 and SX-2 (trademark of and sold by Bioradlaboratories, Richmond, California), XAD-2, XAD-4 (trademark of and soldby Rhom and Haas Co), and Dow Chemical Companies styrene macroreticularcopolymer (20% divinylbenzene). In general, the backbone can compriseany crosslinked or macroreticular polymer having available phenyl rings.Polystyrene containing polymers are preferred.

The catalyst of the instant invention can be prepared, when R is analkyl group containing from 1 to 10 carbon atoms, as follows

(a) a halo-methylated polystyrene is added to Group I metalM-cyclopentadiene wherein M is selected from the group consisting ofsodium, potassium or lithium, in a suitable solvent to form a mixture;

(b) stirring the mixture of (a) for a period of time sufficient toeffect reaction, then filtering the reaction solution and extracting theretained polymer on the filter with a suitable solvent, and drying thepolymer;

(c) stirring the recovered polymer into a suitable solvent and adding analkyl or aryl organolithium material containing from 1 to 10 carbonatoms and containing agitation for a period of time sufficient to effectreaction;

(d) filtering the polymer from solution, readding to a suitable solvent,and adding [Rh(CO)₂ X]₂ wherein X is selected from the group consistingof chlorine, bromine and iodine, and

(e) stirring the material for sufficient time to effect reaction andremoving the catalyst from solution by extracting with a suitablesolvent, and drying prior to use.

The entire synthesis of the catalyst must be carried out under a dryinert atmosphere usually consisting of nitrogen, argon, helium, xenonand neon, and the like. Any recovery and handling is also carried out inan oxygen and water-free environment to prevent catalyst inactivity.Representative examples of suitable solvents in the instant inventionare benzene, tetrahydrofuran (THF), acetophenone, dimethylformamide(DMF) and ethanol/benzene mixtures. All solvents used must be dry andoxygen-free.

Representative examples of the alkyl or aryl organo lithium material aren-butyl lithium, methyl lithium, s-butyl lithium, t-butyl lithium, ethyllithium, propyl lithium, and phenyl lithium.

When the general structural formula of the catalyst has zero anothermethod of preparation is necessary. Generally the procedure comprises,under a dry, inert atmosphere, swelling a halogenated polystyrene with asuitable solvent, cooling and adding sodium, lithium or potassiumcyclopentadieneide together with rapid stirring. The stirred mixture isthen allowed to warm to room temperature and stirring is continued forsufficient time for the reaction to take place. The resulting polymer isthen removed and washed with a suitable solvent, refiltered and redryedyielding a modified polymer having the following structure ##STR4##Procedures for obtaining this polymer can be found at: W.D. Bonds, Jr.,CH Brubaker, Jr., E.S. Chandrasekran, C. Gibbons, R. H. Grubbs, and L.C. Knoll. "Polystyrene Attached Titanocene Species Preparation andReactions", J. Amer Chem Soc., 97, 2128 (1975); J. M. J. Frechet and M.J. Farrall. "Functionalization of Crosslinked Polystyrene Resins byChemical Modification: A Review" from Chemistry and Properties ofCrosslinked Polymer, Academic Press (1977) New York, pp 59, and R. H.Grubbs, "Hybrid-phase Catalysts", Chemtech, 7, 512 (1977).

The recovered polymer is then swollen in a suitable solvent and an alkylor aryl organo lithium material is added. The mixture is stirred for asufficient period of time for reaction to occur and is then filtered,washed with a suitable solvent, and refiltered yielding a materialhaving the general structure ##STR5##

However obtained, the recovered polymer is then added to a suitablesolvent, and a weight of [Rh(CO)₂ X]₂ equal to (0.5) (L) (M) (A) (W) isadded to the stirring solution, wherein;

L is equal to the moles of C₅ H₅ substitution per gram of polymer;

M is equal to the grams of polymer being converted;

A is the present desired rhodium substitution expressed as a decimal;and

W equals the molecular weight of the [Rh(CO)₂ X];Hd 2 compound. The useof this calculation in either catalyst synthesis allows variation of theRh content of the finished catalyst. X represents a halogen such aschlorine, bromine or iodine. Chlorine is the halogen of choice.

The [Rh(CO)₂ X]₂ material is then added to the stirred solution. Thestirring is continued for a sufficient period of time to effect reactionand the filtered product is then extracted with a suitable solvent anddried at high vacuum and room temperature yielding a polymeric catalysthaving the structure. ##STR6##

Representative examples of suitable solvents useful for the extractionsteps of the catalyst synthesis are xylenes, benzene, toluene,tetrahydrofuran and dimethylformamide. However, any solvent which willeffect these functions without destroying the catalyst is, of course,effective.

The invention is more concretely described with reference to theexamples below wherein all parts and percentages are by weight unlessotherwise specified. The examples are provided to exemplify the instantinvention and not to limit it.

Example 1 shows the preparation of the catalyst of the instantinvention. Examples 2, 3, 4, and 5 are subsequent conversions of olefinsto aldehydes using the catalyst of the instant invention, wherein thecatalyst is recovered from one reaction to the next.

EXAMPLE 1

All work was conducted in an argon filled oxygen-free dry box except forthe actual hydroformylation, which was carried out under CO/H₂atmospheres in the autoclave. The solvents employed were of anhydrousgrade and were used without further purification. Five grams of 1%cross-linked chloromethylated polystyrene containing 11 percent chloride(Biorad SX-1, trademark of and sold by Biorad Laboratories, Richmond,California) were added to 3.5 grams (0.0486 moles) of lithiumcyclopentadienide in 100 milliliters (ml) of tetrahydrofuran (THF). Theresulting mixture was stirred for 144 hours and then filtered andextracted with acetone for 18 hours. The polymer was dried at 60° C. ata pressure of 1 torr. Recovery of 5.25 grams of a polymer having thestructure ##STR7## was obtained. Chloride analysis showed the presenceof 0.29% chlorine. This substituted polymer was then stirred in 150 mlof THF for one hour at which time 130 ml of 1.6 molar n-butyl lithiumwas added, and the resulting mixture was stirred in a Schlenk mixingtube (glass-ware designed for air-free handling of sensitive compounds)at 21° C. for 18 hours. The treated polymer was filtered, washed with500 ml of THF, refiltered, added to 200 ml of THF in a Schlenk mixingtube, and 1.5 grams of [Rh(CO)₂ Cl]₂ (0.0077 mole) was added to thestirring polymer. The resulting mixture was stirred for 72 hours, thenfiltered and extracted with benzene for 10 hours. The polymer was driedat 25° C. at 0.01 torr for 24 hours yielding 4.5 grams of catalysthaving the structure ##STR8## wherein P represents the polystyrenepolymer backbone. Chemical analysis showed the rhodium treated polymerto have the structure set forth above, with 5.8% rhodium present.

EXAMPLE 2

In an argon filled dry box a stainless steel autoclave was charged withone gram of the polymeric catalyst described in Example 1 (0.56millimoles rhodium (mMRh) followed by 25 ml of benzene. The catalyst wasallowed to swell for 30 minutes. At the end of this time 35 grams (0.17mole) of 7-tetradecene was added and the reaction pressure was adjustedto 950 pounds per square inch gauge (psig) with a 50/50 mixture ofhydrogen and carbon monoxide. The reaction mixture was heated to 120° C.and stirred for 3 1/2 hours. Product analysis using vapor phasechromatography showed 95% conversion to C₁₅ aldehydes. Fifteen percentof the aldehyde product was identified as n-pentadecanal. Thus it isshown that the catalyst of the instant invention converts a portion ofthe internal olefins to primary aldehydes.

EXAMPLE 3

The catalyst was recovered from Example 2 by filtration and rerunidentically with Example 2 procedure. After 3 1/2 hours of reaction timeanalysis showed 96% conversion of the olefins to C₁₅ aldehydes. Again,about 15% of the entire product was n-pentadecanal.

EXAMPLE 4

The catalyst was recovered from Example 3 by filtration and rerunidentically with Example 2 except that 30 grams of C₁₃,C₁₄ olefinsrecovered from the Olex process (Olex is a trademark of Universal OilProducts Company, designating olefins produced from their Molex process,which is also a trademark of Universal Oil Products). After 5 hours ofreaction time approximately 30% conversion of olefins to aldehydes wasobserved. Olefins contained from the Olex process contain aromatic anddiene contamination.

EXAMPLE 5

The catalyst was recovered from Example 4 by filtration and rerunidentically with Example 2. After four hours of reaction time analysisshowed that 96% conversion of olefins of C₁₅ aldehydes had occured.Again, about 15% of the entire product was n-pentadecanal.

Example 6 and 7 show the effect of a swelling solvent on the polymericbackbone as relates to the efficiency of the catalysts. In Example 6 ahydroformylation conversion of 7-tetradecene was carried out withunswollen catalyst. Example 7 shows swollen catalyst effect on1-dodecene hydroformylation.

EXAMPLE 6

An autoclave in an argon filled glove box was charged with 35 grams(0.17 moles) of 7-tetradecene and 1 gram of catalyst. The reactor wascapped, removed from the glove box, sparged 3 times to 500 pounds persquare inch gauge (psig) with a 1:1 hydrogen/carbon monoxide gas mixtureand heated quickly to 130° C. At maximum temperature the gas pressurewas adjusted to 950 psig. After 5 hours of reaction time 40% of theolefin had been converted to C₁₅ aldehydes. Comparison with the productobtained in Examples 2, 3, and 5 shows the swollen catalyst to be muchmore effective than that of the instant invention.

EXAMPLE 7

The catalyst of Example 6 (1 gram) was swollen in 35 ml of benzene for 2hours. This suspension was then transferred in an argon-filled glove boxto an autoclave and 35 grams (0.208 mole) of 1-dodecene was added to thereactor. The autoclave was capped, removed from the glove box andsparged 3 times to 900 psig with a 1:1 hydrogen/carbon monoxide gasmixture. The reactor was then pressured to 700 psig with the same gasmixture heated quickly to 120° C. and the reactor gas pressure adjustedto 930 psig at maximum temperatures. After 5 hours of reaction time,vapor phase chromatography analysis showed 90% conversion of the olefinto C₁₃ aldehydes.

Example 8 shows the synthesis of the catalyst wherein no intermediatealkyl group is present between the 6-member ring and the 5-member ring.

EXAMPLE 8

The polystyrene described above (1% divinylbenzene crosslinked) wasbrominated according to the procedure taught in the Journal of AmericanChemical Society, Vol. 96, 6469 (1974), Relles and Schluenz, to abromine content of 41%. Thereafter in an argon-filled glove box 10 grams(0.051 mole of bromine) of the brominated polystyrene was swollen in 80mls of anhydrous oxygen-free THF for one hour. The suspension is thencooled to -78° C. and 38 grams of 18% sodium cyclopentadienide is addedover the course of 10 minutes with rapid stirring. The stirred mixtureis allowed to warm to room temperature and stirring is continued for 168hours. The resulting polymer was then filtered and washed with 100 mlsTHF for 1 hour, 150 mls of acetone for 1 hour, 150 mls of CHCl₃ for 1hour, then refiltered and dried at 70° C. at 1 torr. pressure for 12hours. A modified polymer (9.5 grams was collected which had thestructure ##STR9##

Other methods for preparation of the polymer to this point in thesynthesis can be found as previously described. Clearly, a choice ofmethods can be used to this point in the synthesis.

The recovered polymer was then swollen in THF for 1 hour at which time150 mls of 1.6 molar and butyl lithium was slowly added over a 10 minuteperiod. The mixture was stirred for 24 hours and is filtered, washedtwice with 50 ml portions of dry THF and refiltered yielding a polymerhaving the structure ##STR10##

The polymer is then added to 50 mls of dry THF and a weight of [Rh(CO)₂X] equal to (0.5) (L) (M) (A) (W) is added to the stirring solution,wherein L equals moles of C₅ H₅ substitution per gram of polymer, M isequal to grams of polymer being converted, A is the percent desiredrhodium substitution expressed in decimal, W is the molecular weight ofthe [RH(CO)₂ X]₂ compound. After addition, stirring is continued for 120hours. The product is filtered, and the filtered product is extractedwith THF or benzene for from 48 to 72 hours and is dried at 25° C. at0.014 torr for 12 hours, yielding a polymeric catalyst having thestructure ##STR11##

The (pentahaptocyclopentadienyl)biscarbonylrhodium attached to the halomethylated polystyrene has also been found to be an extremely activehydrogenation catalyst at hydrogen pressures of from about 100-3,000pounds per square inch gauge (psig) and temperatures of from 20° C. to140° C. for the reduction of various organic functions. This catalyst isthus a dual catalyst, functioning both as a hydroformylation catalystand a catalyst useful for the reduction of the resulting aldehydes toalcohols. The functions of this catalyst are shown in the examplesbelow. All olefins used were percolated through silica gel before use.

Example 9 shows the reduction of olefins and benzene, example 10 showsthe hydrogenation of a second olefin, example 12 shows hydrogenation ofan aldehyde, and example 13 shows a continuous one-reactor process ofolefin to aldehyde and hydrogenated to alcohol.

EXAMPLE 9

One gram of the catalyst described (containing 4.6% rhodium) was swollenin 35 ml of benzene for 30 minutes. A stainless steel autoclave was thencharged with this resulting suspension and 35.2 grams of 1-dodecene(0.207 moles) was added. The autoclave was capped, removed from theinert atmosphere glove box, sparged 3 times to 500 psig with purehydrogen, and then heated quickly to 110° C. At maximum temperature thehydrogen pressure was adjusted to 600 psig. After 16 minutes of reactiontime vapor phase chromatography (vpc) showed total olefin conversion toalkene. Only n-dodecane and benzene were observed to be present. After30 minutes had passed from the start of the reaction, vpc indicated that16.1% of the benzene present in the reactor had been fully hydrogenatedto cyclohexane.

EXAMPLE 10

The catalyst was recovered from Example 9 and reswollen in 35 ml ofbenzene for 30 minutes. This reaction was carried out identically toExample 1 except that the reaction temperature was lowered to 100° C.and the pressure reduced to 400 psig hydrogen. Vpc indicated that all ofthe 1-dodecene had been converted to n-dodecane after 20 minutes ofreaction time. After 75 minutes of reaction time 33.7% of the benzenepresent in the reactor had been hydrogenated to cyclohexane.

EXAMPLE 11

The catalyst was recovered and reswollen in an identical manner toExample 10 and the reactor identically charged with olefin. The reactionwas carried out identically to Example 9 except that the reactiontemperature was reduced to 80° C. and the reaction pressure reduced to100 psig hydrogen. After 140 minutes reaction time vpc indicated that20% of the olefin had been converted to n-dodecane. The reactionpressure was then increased to 620 psig hydrogen and within 14 minutesof the pressure increase, 100% of the olefin had been hydrogenated ton-dodecane and 10.6% of the benzene solvent had been reduced tocyclohexane.

EXAMPLE 12

The catalyst was recovered and reswollen as described in Example 10. Thereactor was charged with 23.6 grams of aldehyde made from thehydroformylation of 7-tetradecene by this same catalyst under thehydroformylation conditions specified in Examples 2, 3, and 5. Thecatalyst suspension was added, the reactor heated to 110° C., andpressured to 1,000 psig hydrogen. After 2 1/2 hours vpc indicated 93.3%of the C₁₄ -C₁₅ aldehydes had been converted to C₁₄ -C₁₅ alcohols.

EXAMPLE 13

In an argon filled water-free glove box 35 grams of 7-tetradecene (0.178moles) and 1 gram of catalyst were swollen in 35 ml of benzene. Theautoclave was then capped and removed from the box. The reactor waspurged 3 times to 900 psig with a 1:1 gas mixture of CO/H₂ and thenquickly heated to 110° C. Upon attaining maximum temperature the reactorgas pressure was adjusted to 900 psig CO/H₂ and the reaction allowed tocontinue for 320 minutes at which time analysis of the reactor contentsindicated in 95.2% conversion of C₁₄ olefin to C₁₅ aldehydes.

The reactor was then disconnected from the H₂ /CO tank and reconnectedto a source of pure hydrogen. The reactor was purged to 900 psig 12times with hydrogen and reheated to 110° C. When temperature wasreached, the pressure of hydrogen was adjusted to 1000 psig. Thereaction was allowed to continue for 150 minutes at which time analysisindicated a 94% conversion of C₁₅ aldehydes to C₁₅ alcohols.

The instant invention thus provides a hydroformylation catalystcontaining no toxic Group V ligands, yet capable of efficient conversionof internal and primary olefins to aldehydes.

While certain embodiments and details have been shown for the purpose ofillustrating this invention, it will be apparent to those skilled inthis art that various changes and modifications may be made hereinwithout departing from the spirit or the scope of the invention.

I claim:
 1. A method for converting olefins to aldehydes comprisingconverting said olefin in the presence of a catalyst having thestructure ##STR12## wherein R is zero or an alkyl group containing from1 to 10 carbon atoms, and P represents a styrene polymer backbone, saidconversion occurring at a temperature of from about 90° C. to 140° C.and pressures of from about 300 to about 5000 pounds per square inchgauge (psig) in the presence of mixtures of hydrogen and carbonmonoxide.
 2. A method as described in claim 1 wherein the conversion iscarried out in the presence of gases yielding hydrogen, carbon monoxideor mixtures of hydrogen and carbon monoxide.
 3. A method as described inclaim 2 wherein the reaction is carried out in the presence of apolystyrene swelling solvent.
 4. A method as described in claim 3wherein the solvent is selected from the group consisting oftetrahydrofuran, benzene, toluene, xylenes, acetophenone, anddimethylformamide.
 5. A method as described in claim 4 wherein primaryaldehydes are prepared from internal olefins.